US8304580B2 - Method for producing tris(perfluoroalkanesulfonyl)methide acid salt - Google Patents
Method for producing tris(perfluoroalkanesulfonyl)methide acid salt Download PDFInfo
- Publication number
- US8304580B2 US8304580B2 US12/520,178 US52017807A US8304580B2 US 8304580 B2 US8304580 B2 US 8304580B2 US 52017807 A US52017807 A US 52017807A US 8304580 B2 US8304580 B2 US 8304580B2
- Authority
- US
- United States
- Prior art keywords
- fluoride
- chloride
- bromide
- iodide
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
Links
- 239000002253 acid Substances 0.000 title claims abstract description 43
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000003839 salts Chemical class 0.000 title claims abstract description 37
- 239000007983 Tris buffer Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 methylmagnesium halide Chemical class 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 13
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 11
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 claims description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical group 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 10
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 10
- 239000011630 iodine Chemical group 0.000 claims description 10
- 229910052740 iodine Chemical group 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 claims description 10
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 10
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 229940102127 rubidium chloride Drugs 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 5
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 4
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 4
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 claims description 3
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 claims description 3
- KKXPRUXPESLIKJ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;fluoride Chemical compound [F-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KKXPRUXPESLIKJ-UHFFFAOYSA-M 0.000 claims description 3
- JOZHCQBYRBGYAJ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 JOZHCQBYRBGYAJ-UHFFFAOYSA-M 0.000 claims description 3
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims description 3
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims description 3
- WEZAARLTOLBLCR-UHFFFAOYSA-M butyl(triphenyl)phosphanium;fluoride Chemical compound [F-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 WEZAARLTOLBLCR-UHFFFAOYSA-M 0.000 claims description 3
- RQNCKGZETNCAMA-UHFFFAOYSA-M butyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 RQNCKGZETNCAMA-UHFFFAOYSA-M 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 claims description 3
- OYZVNTLRFMXSSC-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;fluoride Chemical compound [F-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 OYZVNTLRFMXSSC-UHFFFAOYSA-M 0.000 claims description 3
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005496 phosphonium group Chemical group 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- HJBZFPLBRXFZNE-UHFFFAOYSA-M tetrabutylphosphanium fluoride hydrofluoride Chemical compound F.[F-].CCCC[P+](CCCC)(CCCC)CCCC HJBZFPLBRXFZNE-UHFFFAOYSA-M 0.000 claims description 3
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 claims description 3
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 3
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 3
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 3
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 3
- GEPYJHDOGKHEMZ-UHFFFAOYSA-M tetraphenylphosphanium;fluoride Chemical compound [F-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GEPYJHDOGKHEMZ-UHFFFAOYSA-M 0.000 claims description 3
- AEFPPQGZJFTXDR-UHFFFAOYSA-M tetraphenylphosphanium;iodide Chemical compound [I-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEFPPQGZJFTXDR-UHFFFAOYSA-M 0.000 claims description 3
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 claims description 3
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010888 waste organic solvent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- SMPAPEKFGLKOIC-UHFFFAOYSA-N oxolane;hydrochloride Chemical compound Cl.C1CCOC1 SMPAPEKFGLKOIC-UHFFFAOYSA-N 0.000 description 4
- JUZCVRZJGRPWJZ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)S(F)(=O)=O JUZCVRZJGRPWJZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZVPDKZBKUGXYRF-UHFFFAOYSA-N cesium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Cs+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F ZVPDKZBKUGXYRF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GCDXWZPDZBWMJA-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O GCDXWZPDZBWMJA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MYIAPBDBTMDUDP-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)C(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F MYIAPBDBTMDUDP-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FBIOXUYLJVKPPG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O FBIOXUYLJVKPPG-UHFFFAOYSA-N 0.000 description 1
- NBFKXQZHVNHRSB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O NBFKXQZHVNHRSB-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- MLRWXKGXSGOAAK-UHFFFAOYSA-N C.C.O=S(=O)(O)O.O=S(=O)=[Rf].O=S(=O)=[Rf].O=S(=O)=[Rf] Chemical compound C.C.O=S(=O)(O)O.O=S(=O)=[Rf].O=S(=O)=[Rf].O=S(=O)=[Rf] MLRWXKGXSGOAAK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- GHAVIAOYNKGAPG-UHFFFAOYSA-N [C-](S(=O)(=O)C(F)(F)F)(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C[N+](C)(C)C Chemical compound [C-](S(=O)(=O)C(F)(F)F)(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C[N+](C)(C)C GHAVIAOYNKGAPG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UVGIYRFIKGLTTI-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane rubidium(1+) Chemical compound [C-](S(=O)(=O)C(F)(F)F)(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[Rb+] UVGIYRFIKGLTTI-UHFFFAOYSA-N 0.000 description 1
- URLJLGCODALCOB-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane tetrapropylazanium Chemical compound [C-](S(=O)(=O)C(F)(F)F)(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C(CC)[N+](CCC)(CCC)CCC URLJLGCODALCOB-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- VRSGGPXTVAQTQE-UHFFFAOYSA-N potassium 1-[bis(1,1,2,2,2-pentafluoroethylsulfonyl)methylsulfonyl]-1,1,2,2,2-pentafluoroethane Chemical compound [C-](S(=O)(=O)C(F)(F)C(F)(F)F)(S(=O)(=O)C(F)(F)C(F)(F)F)S(=O)(=O)C(F)(F)C(F)(F)F.[K+] VRSGGPXTVAQTQE-UHFFFAOYSA-N 0.000 description 1
- RJPWSGDBEHVWPP-UHFFFAOYSA-N potassium bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [K+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F RJPWSGDBEHVWPP-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
- C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Definitions
- Tris(perfluoroalkanesulfonyl)methide acid salt is a substance that is useful as a Lewis acid catalyst or ion conducting material in the fields of organic syntheses, cell electrolyte, etc. Hitherto, there have been known many of the method for producing a tris(perfluoroalkanesulfonyl)methide acid salt, which is the target of the present invention.
- Non-patent Publication 1 discloses that a tris(perfluoroalkanesulfonyl)methide acid salt is obtained by reacting trifluoromethanesulfonyl fluoride with a methylmagnesium halide (Grignard reagent).
- Patent Publication 1 it is a production method, in which a methide acid salt is obtained by one step, and therefore is a very useful method, in contrast with Non-patent Publication 1.
- This method has had a difficulty in industrial production due to that the alkyl metal methane has a high price, that there is a problem of waste since it is treated with hydrochloric acid after the reaction, and that the reaction is conducted at around ⁇ 55° C.
- a method for producing a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1] [Chemical Formula 2] [RfSO 2 ] 3 C n M [1] [In the formula, Rf represents a C 1-9 straight-chain or branched-chain perfluoroalkyl group, n represents an integer that is identical with valence of the corresponding cation, and M is a cation representing an alkali metal, quaternary ammonium represented by (R 1 ) 4 N, or quaternary phosphonium represented by (R 1 ) 4 P.
- R 1 's represent C 1-9 , identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group)], comprising the steps of:
- the target product can be obtained by short steps, easily, and with high selectivity and high yield by directly reacting a tris(perfluoroalkanesulfonyl)methide acid magnesium halide with an alkali metal halide (cesium chloride, potassium chloride, or the like), a quaternary ammonium salt (tetramethylammonium bromide or the like), or a quaternary phosphonium salt (tetrabutylphosphonium bromide or the like), without going through a tris(perfluoroalkanesulfonyl)methide acid (Scheme 2).
- an alkali metal halide cesium chloride, potassium chloride, or the like
- quaternary ammonium salt tetramethylammonium bromide or the like
- a quaternary phosphonium salt tetrabutylphosphonium bromide or the like
- methylmagnesium halide represented by formula [2]
- methylmagnesium iodide methylmagnesium bromide
- methylmagnesium chloride Methylmagnesium chloride is preferable.
- an inert solvent is preferable that does not react with the raw materials and the product during the reaction step. It is possible to cite, for example, ethers such as diethyl ether, diisopropyl ether, t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane, and the like.
- the amount of the solvent used is suitably selected normally from the range of 0.5-10 times by volume, preferably from the range of 5-7 times by volume, methylmagnesium halide represented by formula [2].
- a C 1-9 straight-chain or branched-chain perfluoroalkyl group is normally used, preferably C 1-6 , particularly preferably C 1 (trifluoromethyl group).
- Trifluoromethanesulfonyl fluoride pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutanesulfonyl fluoride, undecafluoropentanesulfonyl fluoride, and tridecafluorohexanesulfonyl fluoride are preferable. Trifluoromethanesulfonyl fluoride is particularly preferable.
- the amount of the perfluoroalkanesulfonyl fluoride is normally 0.75 to 2.0 moles, preferably 0.75 moles to 1.20 moles, particularly preferably 0.8 moles to 1.0 mole, relative to 1 mole of the methylmagnesium halide.
- the present reaction is possible in a temperature range of ⁇ 78° C. to 100° C., preferably ⁇ 10° C. to 60° C.
- a perfluoroalkanesulfonyl fluoride of low-boiling-point it is preferable to conduct that under pressurization, to maintain the reactor at low temperature, or to conduct that by using a condenser of low-temperature.
- the reactor In the case of conducting the reaction under pressurization, the reactor is charged with methylmagnesium halide represented by formula [2] and solvent, then the reactor is sealed, and perfluoroalkanesulfonyl fluoride is added. The addition is conducted, while suitably purging methane produced as a by-product, in order to control pressure.
- the pressure is normally 0.1-10 MPa (absolute pressure, hereinafter the same), preferably 0.1-5 MPa, more preferably 0.1-2 MPa.
- a reactor used upon conducting the reaction under pressurization it is possible to conduct that by using a metal container such as stainless steel, Hastelloy, and Monel.
- a metal container such as stainless steel, Hastelloy, and Monel.
- a person skilled in the art can make a suitable selection regarding the reactor, too.
- the obtained reaction mixture is reacted with at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts, thereby obtaining tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1].
- alkali metal it is possible to cite at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
- lithium fluoride lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide.
- potassium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide are preferable.
- Potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide are particularly preferable.
- R 1 represents C 1-9 , identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups
- the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group
- X represents a halogen (fluorine, chlorine, bromine, or iodine), acetate, alkanesulfonate, or arylsulfonate
- the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or
- quaternary ammonium salt it is possible to use those combined at random, which correspond to the above-mentioned formula.
- tetramethylammonium fluoride tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetramethylammonium fluoride, t
- R 1 represents C 1-9 , identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups
- the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group
- X represents a halogen (fluorine, chlorine, bromine, or iodine), acetate, alkanesulfonate, or arylsulfonate
- the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or
- quaternary phosphonium salt it is possible to use those combined at random, which correspond to the above-mentioned formula.
- tetraphenylphosphonium fluoride tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium fluoride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, butyltriphenylphosphonium fluoride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, trioctylethylphosphonium fluoride, trioctylethylphosphonium chloride, trioctylethylphosphonium bro
- a solvent having high solubility for example, an organic solvent such as ethyl acetate, isopropyl ether, or diethyl ether, and the solvent is distilled out. Then, the after-mentioned recrystallization operation is conducted. With this, it is possible to obtain a tris(perfluoroalkanesulfonyl)methide acid salt of high purity.
- the recrystallization solvent to be used organic solvent or water can be cited.
- organic solvent it can be exemplified by, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, butyl methyl ether, diisopropyl ether, and ethylene glycol dimethyl ether; alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; alkanes such as n-pentane, n-hexane, n-heptane, and n-octane; alkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; hal
- a recrystallization using water is one of particularly preferable embodiments in the industrial production method of the present invention.
- % of the composition analysis values represents “mol %” of compositions obtained by measuring the reaction mixtures by nuclear magnetic resonance analyzer (NMR; in the case of no particular mention, the measurement nuclei is 19 F).
- a 300 ml, glass, reaction container with a condenser was charged with 203 g of 2M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 33 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 17 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 71%).
- a 1000 ml, glass, reaction container with a condenser was charged with 494 g of 1.6M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 64 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 32 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 75%).
- a 300 ml, glass, reaction container with a condenser was charged with 124 g of 1.6M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 16 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 8 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 75.4%).
- Examples 1-6 As are clear in Examples 1-6, as compared with the after-mentioned Reference Example 1, it is possible to easily obtain the target product with high yield by industrially easy methods, such as filtration and recrystallization, with short steps.
- a 300 ml, glass, reaction container with a condenser was charged with 200 g of 2M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 32 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 16 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction.
- waste hydrochloric acid was produced by 232 g as a by-product.
- the obtained organic layer was washed with 450 g of water two times and with 150 g of water, and a liquid separation was conducted (herein, waste water containing organic solvent was produced by 1365 g as a by-product). Then, the organic layer was added to a 500 ml round-bottom flask and was evaporated (waste organic solvent was produced by 123 g as a by-product).
- Example 1 a comparison between Example 1 and Reference Example 1 in the amount of waste liquid is summarized in the following as Table 1.
- Example 1 Comparison in Amount of Waste Liquid (waste liquid or filtrate after recrystallization g/1 g of methide acid salt)
- Example 1 Reference Example 1 Waste organic solvent 0 7.9 (IPE + toluene) Waste water containing THF 5.7 57.9 Waste water containing inorganic salt 10.8 0 Waste liquid in total (g/g) 16.5 65.8 Filtrate after recrystallization (reuse)* 20.8 19.6
- IPE diisopropyl ether
- THF tetrahydrofuran *It shows the amount of the filtrate (usable as a recrystallization solvent of the next reaction) recovered after filtration in the recrystallization step.
- Example 1 can greatly reduce waste liquid as compared with Reference Example 1.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
There is provided a method for producing a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1], including the steps of (a) reacting a methylmagnesium halide represented by formula [2] with a perfluoroalkanesulfonyl fluoride represented by formula [3], thereby obtaining a reaction mixture; and (b) directly reacting the obtained reaction mixture with at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts. By this method, it is possible to easily produce the target methide acid salt with high yield.
Description
This application is a 371 of PCT/JP2007/074296, filed Dec. 18, 2007.
The present invention relates to a method for producing a tris(perfluoroalkanesulfonyl)methide acid salt.
Tris(perfluoroalkanesulfonyl)methide acid salt is a substance that is useful as a Lewis acid catalyst or ion conducting material in the fields of organic syntheses, cell electrolyte, etc. Hitherto, there have been known many of the method for producing a tris(perfluoroalkanesulfonyl)methide acid salt, which is the target of the present invention. For example, Non-patent Publication 1 discloses that a tris(perfluoroalkanesulfonyl)methide acid salt is obtained by reacting trifluoromethanesulfonyl fluoride with a methylmagnesium halide (Grignard reagent).
Furthermore, Patent Publication 1 discloses a method for obtaining a methide acid salt by conducting a reaction between a perfluoroalkanesulfonyl halide and an alkali metal methane in organic solvent.
- Non-patent Publication 1: Inorg. Chem., Vol. 27, pages 2135-2137, 1988
- Patent Publication 1: Japanese Patent Application Publication 2000-226392
In the method of Non-patent Publication 1, as shown in the following scheme, a methide acid magnesium bromide salt produced by a reaction between a Grignard reagent and trifluoromethanesulfonyl fluoride is once turned into a methide acid by sulfuric acid, and furthermore a metal carbonate (herein cesium carbonate) causes this to obtain a methide acid salt (Scheme 1).
[Chemical Formula 1]
4CH3MgBr+3CF3SO2F→MgBr+C(SO2CF3)3 −+3CH4+3MgBrF
MgBr+C(SO2CF3)3 −+H2SO4→HC(SO2CF3)3+BrMgHSO4
HC(SO2CF3)3+½Cs2CO3→CsC(SO2CF3)3+½H2O+½CO2 (Scheme 1)
[Chemical Formula 1]
4CH3MgBr+3CF3SO2F→MgBr+C(SO2CF3)3 −+3CH4+3MgBrF
MgBr+C(SO2CF3)3 −+H2SO4→HC(SO2CF3)3+BrMgHSO4
HC(SO2CF3)3+½Cs2CO3→CsC(SO2CF3)3+½H2O+½CO2 (Scheme 1)
This method, however, has had a burden on productivity and a difficulty somewhat industrially, since the reaction steps are long and since waste treatment takes time due to use of sulfuric acid.
On the other hand, in Patent Publication 1, it is a production method, in which a methide acid salt is obtained by one step, and therefore is a very useful method, in contrast with Non-patent Publication 1. This method, however, has had a difficulty in industrial production due to that the alkyl metal methane has a high price, that there is a problem of waste since it is treated with hydrochloric acid after the reaction, and that the reaction is conducted at around −55° C.
It is an object of the present invention to provide a method for producing a tris(perfluoroalkanesulfonyl)methide acid salt industrially more easily with a lower cost, as compared with conventional production methods.
According to the present invention, there is provided a method for producing a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1]
[Chemical Formula 2]
[RfSO2]3CnM [1]
[In the formula, Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, n represents an integer that is identical with valence of the corresponding cation, and M is a cation representing an alkali metal, quaternary ammonium represented by (R1)4N, or quaternary phosphonium represented by (R1)4P. Herein, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group)], comprising the steps of:
[Chemical Formula 2]
[RfSO2]3CnM [1]
[In the formula, Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, n represents an integer that is identical with valence of the corresponding cation, and M is a cation representing an alkali metal, quaternary ammonium represented by (R1)4N, or quaternary phosphonium represented by (R1)4P. Herein, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group)], comprising the steps of:
(a) reacting a methylmagnesium halide represented by formula [2]
[Chemical Formula 3]
CH3MgX [2]
[In the formula, X represents a chlorine, bromine or iodine.] with a perfluoroalkanesulfonyl fluoride represented by formula [3]
[Chemical Formula 4]
RfSO2F [3]
[In the formula, Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group.], thereby obtaining a reaction mixture; and
[Chemical Formula 3]
CH3MgX [2]
[In the formula, X represents a chlorine, bromine or iodine.] with a perfluoroalkanesulfonyl fluoride represented by formula [3]
[Chemical Formula 4]
RfSO2F [3]
[In the formula, Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group.], thereby obtaining a reaction mixture; and
(b) directly reacting the obtained reaction mixture with at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts.
We have found that a tris(perfluoroalkanesulfonyl)methide acid salt is obtained with short steps and with high purity and high yield, thereby completing the present invention.
According to the method described in Non-patent Publication 1, after a reaction between methylmagnesium halide and perfluoroalkanesulfonyl fluoride, a tris(perfluoroalkanesulfonyl)methide acid magnesium halide represented by formula [4]
[Chemical Formula 5]
[RfSO2]3C(MgX) [4]
[In the formula, Rf is the same as above, and X represents a chlorine, bromine or iodine.]
of a methide acid magnesium bromide salt and the like, which is the obtained reaction mixture, is reacted with sulfuric acid, thereby producing a tris(perfluoroalkanesulfonyl)methide acid represented by formula [5]
[Chemical Formula 6]
[RfSO2]3CH [5]
[In the formula, Rf is the same as above.]
and a metal carbonate (herein cesium carbonate) causes this to obtain a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1]. In this method, however, a burden is placed on productivity, and furthermore purity and yield of the target product lower. Thus, there has been a difficulty even in industrial production.
[Chemical Formula 5]
[RfSO2]3C(MgX) [4]
[In the formula, Rf is the same as above, and X represents a chlorine, bromine or iodine.]
of a methide acid magnesium bromide salt and the like, which is the obtained reaction mixture, is reacted with sulfuric acid, thereby producing a tris(perfluoroalkanesulfonyl)methide acid represented by formula [5]
[Chemical Formula 6]
[RfSO2]3CH [5]
[In the formula, Rf is the same as above.]
and a metal carbonate (herein cesium carbonate) causes this to obtain a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1]. In this method, however, a burden is placed on productivity, and furthermore purity and yield of the target product lower. Thus, there has been a difficulty even in industrial production.
The present inventors, however, have obtained surprising findings that the target product can be obtained by short steps, easily, and with high selectivity and high yield by directly reacting a tris(perfluoroalkanesulfonyl)methide acid magnesium halide with an alkali metal halide (cesium chloride, potassium chloride, or the like), a quaternary ammonium salt (tetramethylammonium bromide or the like), or a quaternary phosphonium salt (tetrabutylphosphonium bromide or the like), without going through a tris(perfluoroalkanesulfonyl)methide acid (Scheme 2).
In the route in which the present invention is used, it is possible to greatly shorten the steps as compared with the past, and an acid such as sulfuric acid is not used. Therefore, it has become possible to greatly reduce a waste liquid, such as waste organic solvent and waste water, which is discharged in the post-treatment step. Furthermore, it has become possible to easily obtain the target product by methods that are even industrially easy, such as filtration and recrystallization.
Thus, it is possible to greatly simplify the steps and the production time. Therefore, it is also possible to easily supply the target product without taking much effort in operation, and it is a very excellent method in terms of production in industrial scale.
According to the present invention, it is possible to produce a tris(perfluoroalkanesulfonyl)methide acid salt, which is useful as organic synthesis and a cell electrolyte, more easily and with higher purity and higher yield as compared with the past. Furthermore, it achieves an effect that can greatly reduce waste liquid, such as waste organic solvent and waste water, which is discharged upon production.
In the following, the present invention is explained in more detail. As specific compounds of methylmagnesium halide represented by formula [2], it is possible to use methylmagnesium iodide, methylmagnesium bromide, and methylmagnesium chloride. Methylmagnesium chloride is preferable.
It is possible to produce methylmagnesium halide, which becomes the raw material, by a conventional publicly known method, but it is also possible to use one on the market as the product. A person skilled in the art can suitably select it.
As an organic solvent usable, an inert solvent is preferable that does not react with the raw materials and the product during the reaction step. It is possible to cite, for example, ethers such as diethyl ether, diisopropyl ether, t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane, and the like. The amount of the solvent used is suitably selected normally from the range of 0.5-10 times by volume, preferably from the range of 5-7 times by volume, methylmagnesium halide represented by formula [2].
For the perfluoroalkanesulfonyl fluoride represented by formula [3], a C1-9 straight-chain or branched-chain perfluoroalkyl group is normally used, preferably C1-6, particularly preferably C1 (trifluoromethyl group). As specific compounds, it is possible to cite trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutanesulfonyl fluoride, undecafluoropentanesulfonyl fluoride, tridecafluorohexanesulfonyl fluoride, pentadecafluoroheptanesulfonyl fluoride, heptadecafluorooctanesulfonyl fluoride, nonadecafluorononanesulfonyl fluoride, and the like. Trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutanesulfonyl fluoride, undecafluoropentanesulfonyl fluoride, and tridecafluorohexanesulfonyl fluoride are preferable. Trifluoromethanesulfonyl fluoride is particularly preferable.
The amount of the perfluoroalkanesulfonyl fluoride is normally 0.75 to 2.0 moles, preferably 0.75 moles to 1.20 moles, particularly preferably 0.8 moles to 1.0 mole, relative to 1 mole of the methylmagnesium halide.
The present reaction is possible in a temperature range of −78° C. to 100° C., preferably −10° C. to 60° C. In the case of using a perfluoroalkanesulfonyl fluoride of low-boiling-point, it is preferable to conduct that under pressurization, to maintain the reactor at low temperature, or to conduct that by using a condenser of low-temperature.
In the case of conducting the reaction under pressurization, the reactor is charged with methylmagnesium halide represented by formula [2] and solvent, then the reactor is sealed, and perfluoroalkanesulfonyl fluoride is added. The addition is conducted, while suitably purging methane produced as a by-product, in order to control pressure.
The pressure is normally 0.1-10 MPa (absolute pressure, hereinafter the same), preferably 0.1-5 MPa, more preferably 0.1-2 MPa.
As to a reactor used upon conducting the reaction under pressurization, it is possible to conduct that by using a metal container such as stainless steel, Hastelloy, and Monel. In the case of conducting the reaction under ordinary pressure, a person skilled in the art can make a suitable selection regarding the reactor, too.
In the present invention, the obtained reaction mixture is reacted with at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts, thereby obtaining tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1].
As the alkali metal, it is possible to cite at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
As specific compounds of the alkali metal halide used in the present invention, it is possible to cite at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide. Sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide are preferable. Potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide are particularly preferable.
As the quaternary ammonium salt used in the present invention, it is possible to cite (R1)4N+.X− (in the formula, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group), X represents a halogen (fluorine, chlorine, bromine, or iodine), acetate, alkanesulfonate, or arylsulfonate (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group). Of these, C1-7 is preferable, and C1-4 is particularly preferable.
As the quaternary ammonium salt, it is possible to use those combined at random, which correspond to the above-mentioned formula. Of those, it is preferable to use tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide.
As the quaternary phosphonium salt used in the present invention, it is possible to cite (R1)4P+.X− (in the formula, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group), X represents a halogen (fluorine, chlorine, bromine, or iodine), acetate, alkanesulfonate, or arylsulfonate (herein, the hydrogen atoms may partially or entirely be replaced with halogen (fluorine, chlorine, bromine, or iodine), alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group). Of these, C1-7 is preferable, and C1-4 is particularly preferable.
As the quaternary phosphonium salt, it is possible to use those combined at random, which correspond to the above-mentioned formula. Of those, it is preferable to use tetraphenylphosphonium fluoride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium fluoride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, butyltriphenylphosphonium fluoride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, trioctylethylphosphonium fluoride, trioctylethylphosphonium chloride, trioctylethylphosphonium bromide, trioctylethylphosphonium iodide, benzyltriphenylphosphonium fluoride, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, ethyltriphenylphosphonium fluoride, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, and ethyltriphenylphosphonium iodide.
In the present invention, methylmagnesium halide represented by formula [2] is reacted with perfluoroalkanesulfonyl fluoride represented by formula [3]. Then, the obtained reaction mixture is directly added to an aqueous solution dissolving at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts to conduct a reaction. After the reaction, the solvent used is distilled out. With this, the target tris(perfluoroalkanesulfonyl)methide acid salt is precipitated.
In the present invention, although details are described hereinafter in Examples, it is possible to easily obtain the methide acid salt with high purity by even industrially easy methods that are filtration and recrystallization.
Then, the filtration step is explained. The filtration step is not particularly limited. Upon this, in the case of a tris(perfluoroalkanesulfonyl)methide acid salt that has low solubility in water, the crystals are precipitated after distilling the solvent out. Therefore, it can be isolated by filtration.
On the other hand, in the case of a salt having high solubility, an extraction is conducted by using a solvent having high solubility to the tris(perfluoroalkanesulfonyl)methide acid salt, for example, an organic solvent such as ethyl acetate, isopropyl ether, or diethyl ether, and the solvent is distilled out. Then, the after-mentioned recrystallization operation is conducted. With this, it is possible to obtain a tris(perfluoroalkanesulfonyl)methide acid salt of high purity.
It is possible to easily remove inorganic salts, which are contained in the methide acid salt and are derived from methylmagnesium halide and alkali metal halide, by conducting the filtration step.
Next, the recrystallization step is explained. Regarding the recrystallization step too, there is no particular limitation. As the recrystallization solvent to be used, organic solvent or water can be cited. As the organic solvent, it can be exemplified by, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, butyl methyl ether, diisopropyl ether, and ethylene glycol dimethyl ether; alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; alkanes such as n-pentane, n-hexane, n-heptane, and n-octane; alkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane and chloroform; and aromatics such as benzene, toluene, and xylene. Each of these organic solvents may be used alone, and a plurality of the organic solvents may be combined.
Of these, as shown in the after-mentioned Examples, even in the case of a recrystallization using water as solvent, it is possible to obtain a tris(perfluoroalkanesulfonyl)methide acid salt of a sufficiently high purity. Therefore, a recrystallization using water is one of particularly preferable embodiments in the industrial production method of the present invention.
By recrystallization, tris(perfluoroalkanesulfonyl)methide acid salt is precipitated. To isolate this, it suffices to conduct a normal operation of organic chemistry. By conducting a filtration operation (Filtration operation referred herein means a filtration operation in the recrystallization step. Hereinafter, the same.), it is possible to obtain a tris(perfluoroalkanesulfonyl)methide acid salt of a still higher purity even as compared with the above-mentioned filtration step.
Furthermore, the present inventors have obtained findings that, since the methide acid salt is partly dissolved in the solution obtained by the filtration operation, it is possible to recover the obtained filtrate and reuse it as a solvent in the recrystallization step (see the after-mentioned Table 1). By reusing, it is possible to further improve yield of tris(perfluoroalkanesulfonyl)methide acid salt and to greatly reduce waste liquid, such as waste organic solvent or waste water, even as compared with the after-mentioned Reference Example. Therefore, productivity has improved remarkably.
By subjecting a solid obtained by the recrystallization operation to vacuum drying, organic solvent or water is removed. With this, tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1] is obtained with high purity.
In the following, the present invention is explained by Examples, but the present invention is not limited by these Examples. Herein, “%” of the composition analysis values represents “mol %” of compositions obtained by measuring the reaction mixtures by nuclear magnetic resonance analyzer (NMR; in the case of no particular mention, the measurement nuclei is 19F).
A 300 ml, glass, reaction container with a condenser was charged with 203 g of 2M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 33 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 17 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 71%).
A 500 ml round-bottom flask was charged with 300 ml of pure water. 17.3 g of cesium chloride was added, and it was completely dissolved. Herein, the obtained reaction liquid was added, and the tetrahydrofuran in the reaction system was distilled out under reduced pressure with an evaporator (herein, 170 g of waste organic solvent was produced as a by-product). With this, cesium tris(trifluoromethanesulfonyl)methide was precipitated. The precipitated crystals were separated by filtration (herein, 320 g of waste water containing inorganic salts was produced as a by-product), followed by recrystallization with 350 g of water. The precipitated crystals were separated by filtration. Recrystallization was conducted again with 260 g of water, and the precipitated crystals were separated by filtration. The obtained crystals were dried. With this, cesium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 29.7 g, a yield of 53% and a purity of 99%.
The reactions were conducted in the same conditions as those of Example 1, except in that rubidium chloride was used in place of cesium chloride (selectivity 76%). As a result, rubidium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 58% and a purity of 99%.
The reactions were conducted in the same conditions as those of Example 1, except in that potassium chloride was used in place of cesium chloride (selectivity 81%). As a result, potassium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 52% and a purity of 99%.
The reactions were conducted in the same conditions as those of Example 1, except in that pentafluoroethanesulfonyl fluoride and potassium chloride were respectively used in place of trifluoromethanesulfonyl fluoride and cesium chloride (selectivity 64%). As a result, potassium tris(pentafluoroethanesulfonyl)methide was obtained with a yield of 46% and a purity of 99%.
A 1000 ml, glass, reaction container with a condenser was charged with 494 g of 1.6M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 64 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 32 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 75%).
A 1000 ml round-bottom flask was charged with 500 ml of pure water. 53.2 g of tetrapropylammonium chloride was added, and it was completely dissolved. Herein, the obtained reaction liquid was added, and the tetrahydrofuran was distilled out under reduced pressure with an evaporator. To the remaining solution, 800 ml of ethyl acetate was added to conduct extraction. The obtained organic layer was evaporated, and the precipitated crystals were subjected to recrystallization with 200 ml of ethanol. The precipitated crystals were separated by filtration. The obtained crystals were dried. With this, tetrapropylammonium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 73.6 g, a yield of 62%, and a purity of 97%.
A 300 ml, glass, reaction container with a condenser was charged with 124 g of 1.6M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 16 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 8 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction (selectivity 75.4%).
A 500 ml round-bottom flask was charged with 250 ml of pure water. 9.2 g of tetramethylammonium bromide was added, and it was completely dissolved. Herein, the obtained reaction liquid was added, and the tetrahydrofuran was distilled out under reduced pressure with an evaporator. To the remaining solution, 200 ml of ethyl acetate was added to conduct extraction. The obtained organic layer was evaporated, and the precipitated crystals were subjected to recrystallization with 300 ml of water. The precipitated crystals were separated by filtration. The obtained crystals were dried. With this, tetramethylammonium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 26.8 g, a yield of 48%, and a purity of 99%.
As are clear in Examples 1-6, as compared with the after-mentioned Reference Example 1, it is possible to easily obtain the target product with high yield by industrially easy methods, such as filtration and recrystallization, with short steps.
A 300 ml, glass, reaction container with a condenser was charged with 200 g of 2M-methylmagnesium chloride-tetrahydrofuran solution under nitrogen gas stream, followed by cooling with ice. Then, 32 g of trifluoromethanesulfonyl fluoride was introduced at an inside temperature of 0-20° C. The temperature was increased once to 35-50° C., and then trifluoromethanesulfonyl fluoride was added again by 16 g. After termination of the addition, it was aged for all night at room temperature to conduct the reaction.
After charging a 500 ml separatory funnel with 200 g of 10% hydrochloric acid, 225 g of the reaction liquid and 72 g of isopropyl ether were added, and a liquid separation operation was conducted (herein, waste hydrochloric acid was produced by 232 g as a by-product). The obtained organic layer was washed with 450 g of water two times and with 150 g of water, and a liquid separation was conducted (herein, waste water containing organic solvent was produced by 1365 g as a by-product). Then, the organic layer was added to a 500 ml round-bottom flask and was evaporated (waste organic solvent was produced by 123 g as a by-product). To the obtained crude methide acid, 200 g of water was added. Toluene was added by 44 g×2, and a liquid separation operation was conducted two times with a separatory funnel (waste organic solvent was produced by 94 g as a by-product). To the obtained aqueous layer, 50% cesium hydroxide aqueous solution was added by 20 g for neutralization and precipitation. Then, a recrystallization was conducted by adding 60 g of water, and the precipitated crystals were separated by filtration. Again, a recrystallization was conducted by 290 g of water, and the precipitated crystals were separated by filtration. The obtained crystals were dried. With this, cesium tris(trifluoromethanesulfonyl)methide was obtained with a yield of 27.6 g and a yield of 52%.
Thus, in Reference Example 1, as compared with Examples 1-6, organic matter and waste water are drained in large amounts in the post-treatment step. Therefore, a burden is placed on industrial operation.
Herein, a comparison between Example 1 and Reference Example 1 in the amount of waste liquid is summarized in the following as Table 1.
| TABLE 1 |
| Comparison in Amount of Waste Liquid (waste liquid or filtrate after |
| recrystallization g/1 g of methide acid salt) |
| Example 1 | Reference Example 1 | ||
| Waste organic solvent | 0 | 7.9 (IPE + toluene) |
| Waste water containing THF | 5.7 | 57.9 |
| Waste water containing inorganic salt | 10.8 | 0 |
| Waste liquid in total (g/g) | 16.5 | 65.8 |
| Filtrate after recrystallization (reuse)* | 20.8 | 19.6 |
| IPE = diisopropyl ether | ||
| THF = tetrahydrofuran | ||
| *It shows the amount of the filtrate (usable as a recrystallization solvent of the next reaction) recovered after filtration in the recrystallization step. | ||
As shown in Table 1, it is understood that Example 1 can greatly reduce waste liquid as compared with Reference Example 1.
Claims (17)
1. A method for producing a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1]
[RfSO2]3CnM [1]
[RfSO2]3CnM [1]
wherein Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, n represents an integer that is identical with valence of the corresponding cation, and
M is a cation representing an alkali metal, quaternary ammonium represented by (R1)4N, or quaternary phosphonium represented by (R1)4P, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups and hydrogen atoms of R1's may partially or entirely be replaced with halogen, alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group, comprising the steps of:
(a) reacting a methylmagnesium halide represented by formula [2]
CH3MgX [2]
CH3MgX [2]
wherein X represents a chlorine, bromine or iodine,
with a perfluoroalkanesulfonyl fluoride represented by formula [3]
RfSO2F [3]
RfSO2F [3]
wherein Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, thereby obtaining a reaction mixture containing a tris(perfluoroalkanesulfonyl)methide acid magnesium halide represented by formula [4]
[RfSO2]3C(MgX) [4]
[RfSO2]3C(MgX) [4]
wherein Rf and X are defined as above; and
(b) directly reacting the tris(perfluoroalkanesulfonyl)methide acid magnesium halide from step (a) with at least one salt selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts, by directly adding the at least one salt to the obtained reaction mixture from step (a),
wherein the quaternary ammonium salts of step (b) are represented by the formula of (R1)4N+.X′− where R1's are defined as above, and X′ represents a halogen, acetate, alkanesulfonate, or arylsulfonate, and hydrogen atoms of X′ may partially or entirely be replaced with halogen, alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group,
wherein the quaternary phosphonium salts of step (b) are represented by the formula of (R1)4P+.X′− where R1's and X′ are defined as above.
2. A method according to claim 1 , wherein the alkali metal as M in formula [1] is at least one selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
3. A method according to claim 1 , wherein the alkali metal halide of the step (b) is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide.
4. A method according to claim 1 , wherein the quaternary ammonium salt of the step (b) is at least one selected from the group consisting of tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide.
5. A method according to claim 1 , wherein the quaternary phosphonium salt of the step (b) is at least one selected from the group consisting of tetraphenylphosphonium fluoride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium fluoride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, butyltriphenylphosphonium fluoride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, trioctylethylphosphonium fluoride, trioctylethylphosphonium chloride, trioctylethylphosphonium bromide, trioctylethylphosphonium iodide, benzyltriphenylphosphonium fluoride, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, ethyltriphenylphosphonium fluoride, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, and ethyltriphenylphosphonium iodide.
6. A method according to claim 1 , wherein the methylmagnesium halide of the step (a) is methylmagnesium chloride.
7. A method according to claim 1 , wherein the perfluoroalkanesulfonyl fluoride of the step (a) is trifluoromethanesulfonyl fluoride.
8. A method according to claim 1 , wherein a product of the step (b) is subjected to filtration and a recrystallization from water.
9. A method for producing a tris(perfluoroalkanesulfonyl)methide acid salt represented by formula [1]
[RfSO2]3CnM [1]
[RfSO2]3CnM [1]
wherein Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, n represents an integer that is identical with valence of the corresponding cation, and
M is a cation representing an alkali metal, quaternary ammonium represented by (R1)4N, or quaternary phosphonium represented by (R1)4P, R1's represent C1-9, identical or different, straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon groups or aryl groups, and hydrogen atoms of R1's may partially or entirely be replaced with halogen, alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group, consisting of the steps of:
(a) reacting a methylmagnesium halide represented by formula [2]
CH3MgX [2]
CH3MgX [2]
wherein X represents a chlorine, bromine or iodine,
with a perfluoroalkanesulfonyl fluoride represented by formula [3]
RfSO2F [3]
RfSO2F [3]
wherein Rf represents a C1-9 straight-chain or branched-chain perfluoroalkyl group, thereby obtaining a reaction mixture; and
(b) directly reacting the obtained reaction mixture from step (a) with at least one salt selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quaternary phosphonium salts,
wherein the quaternary ammonium salts of step (b) are represented by the formula of (R1)4N+.X′− where R1's are defined as above, and X′ represents a halogen, acetate, alkanesulfonate, or arylsulfonate, and hydrogen atoms of X′ may partially or entirely be replaced with halogen, alkyl group, amino group, nitro group, acetyl group, cyano group or hydroxyl group,
wherein the quaternary phosphonium salts of step (b) are represented by the formula of (R1)4P+.X′− where R1's and X′ are defined as above.
10. The method according to claim 9 , wherein the obtained reaction mixture from step (a) comprises a tris(perfluoroalkanesulfonyl)methide acid magnesium halide represented by formula [4]
[RfSO2] 3C(MgX) [4]
[RfSO2] 3C(MgX) [4]
wherein Rf is the same as above, and X represents a chlorine, bromine or iodine.
11. The method according to claim 9 , wherein the alkali metal as M in formula [1] is at least one selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
12. The method according to claim 9 , wherein the alkali metal halide of the step (b) is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide.
13. The method according to claim 9 , wherein the quaternary ammonium salt of the step (b) is at least one selected from the group consisting of tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide.
14. The method according to claim 9 , wherein the quaternary phosphonium salt of the step (b) is at least one selected from the group consisting of tetraphenylphosphonium fluoride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium fluoride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, butyltriphenylphosphonium fluoride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, trioctylethylphosphonium fluoride, trioctylethylphosphonium chloride, trioctylethylphosphonium bromide, trioctylethylphosphonium iodide, benzyltriphenylphosphonium fluoride, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, ethyltriphenylphosphonium fluoride, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, and ethyltriphenylphosphonium iodide.
15. The method according to claim 9 , wherein the methylmagnesium halide of the step (a) is methylmagnesium chloride.
16. The method according to claim 9 , wherein the perfluoroalkanesulfonyl fluoride of the step (a) is trifluoromethanesulfonyl fluoride.
17. The method according to claim 9 , wherein a product of the step (b) is subjected to filtration and a recrystallization from water.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| JP2006-342043 | 2006-12-20 | ||
| JP2006342043 | 2006-12-20 | ||
| JP2007317315 | 2007-12-07 | ||
| JP2007-317315 | 2007-12-07 | ||
| JP2007324490A JP5186910B2 (en) | 2006-12-20 | 2007-12-17 | Method for producing tris (perfluoroalkanesulfonyl) methidoate |
| JP2007-324490 | 2007-12-17 | ||
| PCT/JP2007/074296 WO2008075672A1 (en) | 2006-12-20 | 2007-12-18 | Method for producing tris(perfluoroalkanesulfonyl)methide acid salt |
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| Publication Number | Publication Date |
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| US20100022803A1 US20100022803A1 (en) | 2010-01-28 |
| US8304580B2 true US8304580B2 (en) | 2012-11-06 |
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| US12/520,178 Expired - Fee Related US8304580B2 (en) | 2006-12-20 | 2007-12-18 | Method for producing tris(perfluoroalkanesulfonyl)methide acid salt |
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| Country | Link |
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| US (1) | US8304580B2 (en) |
| EP (1) | EP2080753B1 (en) |
| JP (1) | JP5186910B2 (en) |
| KR (1) | KR101030639B1 (en) |
| CN (1) | CN101553465B (en) |
| AT (1) | ATE545628T1 (en) |
| WO (1) | WO2008075672A1 (en) |
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| JP2010536722A (en) * | 2007-08-16 | 2010-12-02 | ロンザ リミテッド | Process for producing and purifying alkali metal and alkaline earth metal tricyanomethanides |
| US8377406B1 (en) | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
| CN115124051A (en) * | 2021-03-24 | 2022-09-30 | 上海如鲲新材料股份有限公司 | Preparation method and application of fluorosulfonate |
| CN115557862A (en) * | 2022-10-25 | 2023-01-03 | 广州天赐高新材料股份有限公司 | Preparation method of tris (perfluoroalkyl sulfonyl) methane and lithium salt thereof |
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| US5273840A (en) * | 1990-08-01 | 1993-12-28 | Covalent Associates Incorporated | Methide salts, formulations, electrolytes and batteries formed therefrom |
| JP2000226392A (en) | 1999-02-03 | 2000-08-15 | Kanto Denka Kogyo Co Ltd | Production of tris(perfluoroalkylsulfonyl)methide salt |
| EP0813521B1 (en) * | 1995-03-06 | 2000-09-13 | Minnesota Mining And Manufacturing Company | Energy-activatable salts with fluorocarbon anions |
| JP2000256348A (en) | 1999-03-12 | 2000-09-19 | Asahi Chem Ind Co Ltd | Production of epsilon-caprolactone |
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-
2007
- 2007-12-17 JP JP2007324490A patent/JP5186910B2/en not_active Expired - Fee Related
- 2007-12-18 CN CN2007800443794A patent/CN101553465B/en not_active Expired - Fee Related
- 2007-12-18 AT AT07850784T patent/ATE545628T1/en active
- 2007-12-18 US US12/520,178 patent/US8304580B2/en not_active Expired - Fee Related
- 2007-12-18 KR KR1020097014626A patent/KR101030639B1/en active IP Right Grant
- 2007-12-18 EP EP07850784A patent/EP2080753B1/en not_active Not-in-force
- 2007-12-18 WO PCT/JP2007/074296 patent/WO2008075672A1/en active Application Filing
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| US5273840A (en) * | 1990-08-01 | 1993-12-28 | Covalent Associates Incorporated | Methide salts, formulations, electrolytes and batteries formed therefrom |
| EP0813521B1 (en) * | 1995-03-06 | 2000-09-13 | Minnesota Mining And Manufacturing Company | Energy-activatable salts with fluorocarbon anions |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2080753A1 (en) | 2009-07-22 |
| EP2080753A4 (en) | 2011-07-06 |
| JP2009155206A (en) | 2009-07-16 |
| JP5186910B2 (en) | 2013-04-24 |
| ATE545628T1 (en) | 2012-03-15 |
| WO2008075672A1 (en) | 2008-06-26 |
| KR101030639B1 (en) | 2011-04-20 |
| KR20090101234A (en) | 2009-09-24 |
| US20100022803A1 (en) | 2010-01-28 |
| EP2080753B1 (en) | 2012-02-15 |
| CN101553465B (en) | 2012-07-18 |
| CN101553465A (en) | 2009-10-07 |
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